EP0679934B1 - Verfahren zru herstellung eines photographischen Materials, das zur Verwendung in Phototypieanwendungen geeignet ist - Google Patents

Verfahren zru herstellung eines photographischen Materials, das zur Verwendung in Phototypieanwendungen geeignet ist Download PDF

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Publication number
EP0679934B1
EP0679934B1 EP19950200646 EP95200646A EP0679934B1 EP 0679934 B1 EP0679934 B1 EP 0679934B1 EP 19950200646 EP19950200646 EP 19950200646 EP 95200646 A EP95200646 A EP 95200646A EP 0679934 B1 EP0679934 B1 EP 0679934B1
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EP
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Prior art keywords
silver halide
halide emulsion
silver
mole
layer
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EP19950200646
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English (en)
French (fr)
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EP0679934A3 (de
EP0679934A2 (de
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Jos C/O Agfa-Gevaert N.V. Vaes
Luc C/O Agfa-Gevaert N.V. Wabbes
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Agfa Gevaert NV
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Agfa Gevaert NV
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/06—Silver salts
    • G03F7/07—Silver salts used for diffusion transfer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/015—Apparatus or processes for the preparation of emulsions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising

Definitions

  • the present invention relates to a method for making a silver halide photographic material sensitive to high intensity-short time exposure and especially to a method for making such a material that can be used for obtaining a lithographic printing plate according to the silver salt diffusion transfer process and to a method for obtaining said lithographic printing plate.
  • Such systems are, for example, high speed phototypesetting systems according to which information output from an electronic computer is immediately displayed as letters or figures by a cathode ray tube and press facsimile systems for rapid transmission of newspaper originals to a remote place.
  • phototypesetters usually work with a He/Ne laser (632nm), laser diode (650 nm or 680nm) or LED (670nm or 780nm). Especially phototypesetters that operate with a He/Ne laser or LED are frequently employed, but also argon lasers (488 nm) are still in use.
  • a photographic material for a photographic material to be suitable for use in phototypesetting applications it is required that the material is of high speed to so-called high intensity-short time exposure (flash exposure or scanning exposure), namely exposure for 10 -4 second or less and yields images of high contrast and high resolving power.
  • flash exposure or scanning exposure namely exposure for 10 -4 second or less
  • Photographic phototypesetting materials include photographic films and papers used in a process for preparing a lithographic printing plate and silver salt diffusion transfer based (hereinafter called DTR-) lithographic printing plates disclosed in e.g. US-P-4,501,811 and US-P-4,784,933. With the latter materials a lithographic printing plate is immediately obtained without the need of a contact exposure or camera exposure.
  • DTR- silver salt diffusion transfer based
  • a photographic DTR material preferably comprises a silver halide emulsion mainly consisting of silver chloride in order to obtain a sufficiently high rate of solution of the silver halide and a satisfactory gradation necessary for graphic purposes. Only a small amount of silver bromide and/or silver iodide usually not exceeding 5 mole % is present. However as a consequence of the lower energy output of some lasers, e.g. laserdiodes, the sensitivity of these conventional silver chloride DTR emulsions is no longer sufficient when using those types of laser as exposure unit as disclosed in US-P-5,059,508.
  • An image with a low minimal and a high maximal density and a high contrast results in a better sharpness.
  • the photographic material is to be used in a silver salt diffusion transfer process and especially for preparing printing plates according to this process it is necessary to obtain a silver image with lower minimal and/or higher maximal density and/or higher contrast to improve the printing properties i.a. higher printing endurance, better ink acceptance in the printing areas, less ink acceptance in the non printing areas both during start-up of the printing process (toning) and during printing (staining), sharper prints.
  • the activity of the built-in iridium complex depends enormously on the conditions during its addition. It is known that the initial ligands of commercially available iridium complexes can exchange with other ligands (water, hydroxyl ions, etc.). This exchange reaction happens whenever the halogen complex is dissolved and the rate is very much depending on the temperature, the acidity, the amount of free silver ions etc. of the medium. So, said activity is therefore unpredictable when the iridium complex is added during the physical ripening and surely during the precipitation of a silver halide emulsion when the above mentioned parameters are constantly changing. So the possibility of adding the iridium complex to the silver halide emulsion under well defined conditions would be a much appreciated improvement.
  • EP-A 568.091 discloses a process reducing reciprocity failure of a silver chloride emulsion comprising adding iridium and bromide to said chloride emulsion wherein said bromide is added simultaneously or after said iridium. This document does not disclose a method for obtaining an image with a higher contrast. Furthermore, the addition of said bromide is an additional step in the preparation of said emulsion and can easily leads to irreproducible photographic results due to the partial conversion of silver chloride to silver bromide in said silver chloride emulsion.
  • a method for obtaining a photographic material by coating on a support at least one layer comprising at least one photosensitive silver halide emulsion the preparation of said photosensitive silver halide emulsion comprising the steps of (i) formation of a silver halide emulsion by precipitation of silver halide crystals in an aqueous medium, (ii) physical ripening of said silver halide emulsion, (iii) desalination of said silver halide emulsion and (iv) chemical ripening of said silver halide emulsion, the silver halide crystals of said photosensitive silver halide emulsion containing silver chloride for at least 60 mole%, silver bromide in a range from 2 mole % to 40 mole % and silver iodide in a range from 0 mole % to 1 mole %, characterized in that a water soluble iridium compound is added between the end of the physical
  • an imaging element by coating on a support at least one silver halide emulsion layer as defined above and an image receiving layer containing physical development nuclei in water permeable relationship with said silver halide emulsion layer.
  • a method for obtaining a lithographic printing plate according to the silver salt diffusion transfer process comprising image-wise exposing with a high intensity-short time exposure an imaging element as described above and developing said imaging element using an alkaline processing liquid in the presence of developing agent(s) and a silver halide solvent.
  • a silver halide photographic material having a high sensitivity to high intensity-short time exposure can be made by coating on a support at least one silver halide emulsion wherein the silver halide crystals contain silver chloride for at least 60 mole%, silver bromide in a range from 2 mole % to 40 mole % and silver iodide in a range from 0 mole % to 1 mole %, when a water soluble iridium compound is added between the end of the physical ripening and the end of the chemical ripening to said silver halide emulsion at the above defined conditions.
  • Said photographic material yields images of good quality, especially of high contrast.
  • a lithographic printing plate according to the silver salt diffusion transfer process can be obtained by image-wise exposing with a high intensity-short time exposure an imaging element containing such an silver halide emulsion.
  • the diameter of a silver halide grain is meant the diameter of a sphere with an equivalent volume as the corresponding silver halide grain.
  • the number average diameter r of the silver halide grains is the average of all these diameters. Furtheron, when there is referred to the diameter of a silver halide grain or to the average diameter r of the silver halide grains there is always meant the diameter,respectively the average diameter of (a) silver halide grain(s) as determined by this last method.
  • Chemical ripening or sensitization of a silver halide emulsion is the process wherein the speed of the silver halide emulsion is increased by adding specific compounds and/or changing the silver halide emulsion conditions such as pH, pAg, temperature, etc. .
  • the chemical ripening is ended when the speed and the fog of the silver halide emulsion change no longer, what is mostly effected by adding specific compounds and/or lowering the temperature of the silver halide emulsion.
  • the water soluble iridium compound may be added at any time between the end of the physical ripening and the end of the chemical ripening to said silver halide emulsion provided said silver halide emulsion has a pH between 4 and 6.5, a pCl between -0.3 and 1 and a ratio by weight of gelatin to silver halide, expressed as equivalent amount of silver nitrate between 0.05 and 0.5 e.g. after the physical ripening but before, during or after the desalination of the silver halide emulsion, at the beginning or during the chemical ripening.
  • the water soluble iridium compound is added between the end of the physical ripening and the beginning of the chemical ripening, more preferably between the end of the physical ripening and before the desalination of the silver halide emulsion.
  • the silver halide emulsion has a pH between 4 and 6.5, more preferably between 4.3 and 5.5, most preferably between 4.5 and 5.2.
  • the pCl of said silver halide emulsion is comprised between- 0.3 and 1, more preferably between- 0.2 and 0.5, most preferably between -0.15 and 0.15.
  • the ratio by weight of gelatin to silver halide, expressed as equivalent amount of silver nitrate lies between 0.05 and 0.5, more preferably between 0.1 and 0.4, most preferably between 0.15 and 0.25.
  • water soluble iridium compounds various compounds may be used such as iridium chloride (IrCl 3 or IrCl 4 ), hexachloroiridic acid (III) or salts thereof, hexachloroiridic acid (IV) or salts thereof, etc..
  • concentration of the water soluble iridium compound added between the end of the physical ripening and the end of the chemical ripening ranges from 10 -8 to 10 -3 mole per mole AgNO 3 , more preferably from 10 -7 to 10 -5 mole per mole AgNO 3 .
  • the amount of bromide or iodide added to the silver halide emulsion simultaneously or after the addition of the water soluble iridium compound to said emulsion is preferably less than 0.3 mole/mole AgX, more preferably less than 0.2 mole/mole AgX, most preferably substantially 0 mole/mole AgX.
  • the silver halide emulsion comprises principally silver chloride while a fraction of silver bromide is present ranging from 2 mole % to 40 mole %, and of silver iodide ranging from 0 mole % mole % to 1 mole %.
  • said fraction of silver bromide ranges from 12 mole % to 35 mole %, more preferably from 15 mole % to 25 mole %.
  • the silver halide emulsion preferably belongs to the core/shell type well known to those skilled in the art in the sense that substantially all the bromide is concentrated in the core. This core contains preferably 10 to 40 % of the total silver halide precipitated, while the shell consists preferably of 60 to 90 % of the total silver halide precipitated.
  • the photographic silver halide emulsion(s) for coating a silver halide emulsion layer in accordance with the present invention can be prepared according to different methods as described e.g. by P. Glafkides in "Chimie et Physique Photographique", Paul Montel, Paris (1967), by G.F. Duffin in “Photographic Emulsion Chemistry", The Focal Press, London (1966), and by V.L. Zelikman et al in “Making and Coating Photographic Emulsion", The Focal Press, London (1966).
  • the precipitation of the silver halide crystals is carried out by mixing soluble silver salts and soluble halides, preferably under such conditions that at the end of the precipitation the number average grain size r of the silver halide crystals is at least 50 %, more preferably at least 75 % of the number average grain size of the silver halide crystals of the photographic silver halide emulsion.
  • said silver halide emulsion is physically ripened.
  • the photosensitive silver halide emulsion(s) can also be prepared under Ostwald growth conditions, by continuously adding fine grains to the reaction vessel. The grains are grown in the absence or in the presence of any product having a site-directing activity.
  • a rhodium containing compound is usually added to the silver halide emulsion, preferably during the precipitation stage, more preferably between the addition of 0 mole % and 60 mole % of the silver salt, most preferably between the addition of 2 mole % and 35 mole % of the silver salt.
  • the concentration of the added rhodium compound(s) preferably range(s) from 10 -8 to 10 -3 mole per mole of AgNO 3 , more preferably from 0.5*10 -7 to 10 -5 mole per mole of AgNO 3 .
  • the rhodium containing compound may also be added at any other time during the silver halide emulsion preparation, e.g. before or after any of the well known desalting stages of the silver halide emulsion, before or after adding any supplementary colloid binder, before or after any spectral or chemical sensitization or stabilization stage, etc..
  • an iridium containing compound may be added to the silver halide emulsion at any time during the silver halide emulsion preparation after the end of the chemical ripening and/or when the silver halide emulsion conditions of pH, pCl or ratio by weight of gelatin to silver halide, expressed as equivalent amount of silver nitrate, do not correspond to the silver halide emulsion conditions in accordance with the present invention.
  • the silver halide emulsion is chemically sensitized e.g. by adding sulphur-containing compounds during the chemical ripening stage e.g. allyl isothiocyanate, allyl thiourea, and sodium thiosulphate.
  • reducing agents e.g. the tin compounds described in BE-A-493,464 and 568,687, and polyamines such as diethylene triamine or derivatives of aminoethane-sulphonic acid can be used as chemical sensitizers.
  • Other suitable chemical sensitizers are noble metals and noble metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium. This method of chemical sensitization has been described in the article of R. Koslowsky, Z. Wiss. Photogr. Photophys. Photochem. 46, 65-72 (1951).
  • the silver halide emulsion is desalted by one of the well known techniques e.g. by flocculating said silver halide emulsion, washing it with water or an aqueous solution and redispersing it, by ultrafiltration, etc..
  • the desalination of the silver halide emulsion is carried out before the chemical ripening of the silver halide emulsion, but can also be carried out afterwards.
  • the average size of the silver halide grains in the photosensitive silver halide emulsion may range from 0.10 to 0.70 ⁇ m, preferably from 0.25 to 0.45 ⁇ m.
  • the silver halide emulsion can be spectrally sensitized according to the spectral emission of the exposure source for which the photographic element is designed.
  • Suitable sensitizing dyes for the visible spectral region include methine dyes such as those described by F.M. Hamer in "The Cyanine Dyes and Related Compounds", 1964, John Wiley & Sons. Dyes that can be used for this purpose include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, homopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes, complex merocyanine dyes.
  • a green sensitizing dye is needed.
  • a blue sensizing dye is incorporated.
  • a red light emitting source e.g. a LED or a HeNe laser
  • a red sensitizing dye is used.
  • special spectral sensitizing dyes suited for the near infra-red are required. Suitable infra-red sensitizing dyes are disclosed in i.a. US-P 2,095,854, 2,095,856, 2,955,939, 3,482,978, 3,552,974, 3,573,921, 3,582,344, 3,623,881 and 3,695,888.
  • a preferred blue sensitizing dye, green sensitizing dye, red sensitizing dye and infra-red sensitizing dye in connection with the present invention are described in EP-A 554,585.
  • supersensitizers in combination with red or infra-red sensitizing dyes.
  • Suitable supersensitizers are described in Research Disclosure Vol 289, May 1988, item 28952.
  • the spectral sensitizers can be added to the photographic silver halide emulsions in the form of an aqueous solution, a solution in an organic solvent or in the form of a dispersion.
  • the silver halide emulsions may contain the usual emulsion stabilizers.
  • Suitable silver halide emulsion stabilizers are azaindenes, preferably tetra- or penta-azaindenes, especially those substituted with hydroxy or amino groups. Compounds of this kind have been described by BIRR in Z. Wiss. Photogr. Photophys. Photochem. 47, 2-27 (1952).
  • Other suitable silver halide emulsion stabilizers are i.a. heterocyclic mercapto compounds e.g. phenylmercaptotetrazole, quaternary benzothiazole derivatives, and benzotriazole.
  • the silver halide emulsions may contain pH controlling ingredients.
  • the silver halide emulsion layer is coated at a pH value near the isoelectric point of the gelatin to improve the stability characteristics of the coated layer.
  • Other ingredients such as antifogging agents, development accelerators, preferably polyalkyleneoxide derivatives having a molecular weight of at least 400 such as those described in e.g. US-P 3,038,805, 4,038,075 and 4,292,400, wetting agents and hardening agents for gelatin may be present.
  • the silver halide emulsion layer may comprise light-screening dyes that absorb scattering light and thus promote the image sharpness. Suitable light-absorbing dyes are described in i.a. US-P 4,092,168, US-P 4,311,787, DE-P 2,453,217.
  • compositions, preparation and coating of silver halide emulsions can be found in e.g. Product Licensing Index, Vol. 92. December 1971, publication 9232, p. 107-109.
  • the photographic material of the present invention may contain additional hydrophilic layers, in water permeable relationship with the photosensitive silver halide emulsion layer.
  • Layers being in waterpermeable contact with each other are layers that are contiguous to each other or only separated from each other by (a) waterpermeable layer(s).
  • the nature of a waterpermeable layer is such that it does not substantially inhibit or restrain the diffusion of water or of compounds contained in an aqueous solution e.g. developing agents or complexed silver ions.
  • a base-layer between the support and the photosensitive silver halide emulsion layer.
  • said base-layer serves as an antihalation layer.
  • This layer can therefore contain the same light-absorbing dyes as described above for the silver halide emulsion layer ; as alternative finely divided carbon black can be used for the same antihalation purposes as described in US-P 2,327,828.
  • light reflecting pigments e.g. titaniumdioxide can be present.
  • this layer can contain hardening agents, matting agents, e.g. silica particles, and wetting agents.
  • these matting agents and/or light reflection pigments may also be present in the silver halide emulsion layer the most part however preferably being present in said base-layer.
  • the light reflecting pigments may be present in a separate layer provided between the antihalation layer and the photosensitive silver halide emulsion layer.
  • a backing layer is provided at the non-light sensitive side of the support.
  • This layer which can serve as anti-curl layer can contain i.a. matting agents e.g. silica particles, lubricants, antistatic agents, light absorbing dyes, opacifying agents, e.g. titanium oxide and the usual ingredients like hardeners and wetting agents.
  • the backing layer can consist of one single layer or a double layer pack.
  • the hydrophilic layers usually contain gelatin as hydrophilic colloid binder. Mixtures of different gelatins with different viscosities can be used to adjust the rheological properties of the layer. Like the silver halide emulsion layer the other hydrophilic layers are coated preferably at a pH value near the isoelectric point of the gelatin. But instead of or together with gelatin, use can be made of one or more other natural and/or synthetic hydrophilic colloids, e.g. albumin, casein, zein, polyvinyl alcohol, alginic acids or salts thereof, cellulose derivatives such as carboxymethyl cellulose, modified gelatin, e.g. phthaloyl gelatin etc.
  • other natural and/or synthetic hydrophilic colloids e.g. albumin, casein, zein, polyvinyl alcohol, alginic acids or salts thereof, cellulose derivatives such as carboxymethyl cellulose, modified gelatin, e.g. phthaloyl gelatin etc.
  • the hydrophilic layers of the photographic element can be hardened with appropriate hardening agents such as those of the vinylsulfone type e.g. methylenebis(sulfonylethylene), aldehydes e.g. formaldehyde, glyoxal, and glutaraldehyde, N-methylol compounds e.g. dimethylolurea and methyloldimethylhydantoin, active halogen compounds e.g. 2,4-dichloro-6-hydroxy-s-triazine, and mucohalogenic acids e.g. mucochloric acid and mucophenoxychloric acid.
  • hardeners can be used alone or in combination.
  • the binders can also be hardened with fast-reacting hardeners such as carbamoylpyridinium salts of the type, described in US 4,063,952.
  • Preferably used hardening agents are of the aldehyde type.
  • the hardening agents can be used in wide concentration range but are preferably used in an amount of 4% to 7% of the hydrophilic colloid. Different amounts of hardener can be used in the different layers of the imaging element or the hardening of one layer may be adjusted by the diffusion of a hardener from another layer.
  • the imaging element used according to the present invention may further comprise various kinds of surface-active agents in the photographic silver halide emulsion layer or in at least one other hydrophilic colloid layer.
  • suitable surface-active agents are described in e.g. EP 545452.
  • compounds containing perfluorinated alkyl groups are used.
  • the photographic material of the present invention may further comprise various other additives such as e.g. compounds improving the dimensional stability of the photographic element, UV-absorbers, spacing agents and plasticizers.
  • Supports suitable for use in accordance with the present invention may be opaque or transparent, e.g. a paper support or resin support.
  • a paper support preference is given to one coated at one or both sides with an Alpha-olefin polymer, e.g. a polyethylene layer which optionally contains an anti-halation dye or pigment.
  • an organic resin support e.g. poly(ethylene terephthalate) film or poly-Alpha-olefin films such as polyethylene or polypropylene film.
  • the thickness of such organic resin film is preferably comprised between 0.07 and 0.35 mm.
  • These organic resin supports are preferably coated with a hydrophilic adhesion layer which can contain water insoluble particles such as silica or titanium dioxide.
  • Metal supports e.g. aluminum may also be used in accordance with the present invention.
  • the above described photographic material element is information-wise exposed using a scanning exposure beam and is subsequently developed in an alkaline processing liquid in the presence of developing agents.
  • Silver halide developing agents for use in accordance with the present invention are preferably of the p-dihydroxybenzene type, e.g. hydroquinone, methylhydroquinone or chlorohydroquinone, preferably in combination with an auxiliary developing agent being a 1-phenyl-3-pyrazolidinone-type developing agent and/or p-monomethylaminophenol.
  • Particularly useful auxiliary developing agents are of the phenidone type e.g. 1-phenyl-3-pyrazolidinone, 1-phenyl-4-monomethyl-3-pyrazolidinone, and 1-phenyl-4,4-dimethyl-3-pyrazolidinone.
  • Said developing agents may be contained in an alkaline processing liquid but are preferably contained in one or more layers of the photographic element. In the latter case the alkaline processing liquid merely serves as an alkaline activating liquid.
  • the pH of said alkaline liquid is preferably between 9 and 14, more preferably between 10 and 13 and may be established by an organic and/or inorganic alkali agent.
  • suitable alkali agents are e.g. sodium hydroxide, carbonates, phosphates, alkanolamines or mixtures thereof.
  • the alkaline processing liquid preferably also contains a preserving agent having antioxidation activity, e.g. sulphite ions. Further may be present a thickening agent, fog inhibiting agents, calcium-sequestering compounds, anti-sludge agents, development accelerators and hardeners including latent hardeners.
  • a preserving agent having antioxidation activity e.g. sulphite ions.
  • a thickening agent e.g. sulphite ions
  • fog inhibiting agents e.g., calcium-sequestering compounds, anti-sludge agents, development accelerators and hardeners including latent hardeners.
  • the above described development step is preferably followed by a washing step, a fixing step and another washing or stabilizing step.
  • the first washing step may be omitted.
  • the above described photographic material obtained according to the present invention may yield an image according to the silver salt diffusion transfer process.
  • DTR-process The principles of the silver complex diffusion transfer reversal process, hereinafter called DTR-process, have been described e.g. in US-P-2,352,014 and the book “Photographic Silver Halide Diffusion Processes” by André Rott and Edith Weyde - The Focal Press -London and New York, (1972).
  • non-developed silver halide of an information-wise exposed photographic silver halide emulsion layer material is transformed with a so-called silver halide solvent into soluble silver complex compounds which are allowed to diffuse into an image receiving element and are reduced therein with a developing agent, generally in the presence of physical development nuclei, to form a silver image having reversed image density values ("DTR-image") with respect to the black silver image obtained in the exposed areas of the photographic material.
  • a developing agent generally in the presence of physical development nuclei
  • a DTR-image bearing material can be used as a planographic printing plate wherein the DTR-silver image areas form the water-repellent ink-receptive areas on a water-receptive ink-repellent background.
  • the DTR-image can be formed in the image receiving layer of a sheet or web material which is a separate element with respect to the photographic silver halide emulsion material (a so-called two-sheet DTR element) or in the image receiving layer of a so-called single-support-element, also called mono-sheet element, which contains at least one photographic silver halide emulsion layer integral with an image receiving layer in waterpermeable relationship therewith. It is the latter mono-sheet version which is preferred for the preparation of offset printing plates by the DTR method.
  • Suitable silver complexing agents also called silver halide solvents for use in accordance with the present invention are e.g. thiosulphate or thiocyanate in an amount ranging from 5 g to 20 g per liter.
  • Other interesting silver halide complexing agents are e.g. sulphite, amines, 2-mercaptobenzoic acid, cyclic imide compounds such as e.g. uracil, 5,5-dialkylhydantoins, alkyl sulfones and oxazolidones.
  • alkanolamines for use in connection with the present invention are alkanolamines.
  • Said alkanolamines may be present in the alkaline processing liquid in a concentration preferably between 0.1% and 5% by weight. However part or all of the alkanolamine can be present in one or more layers of the imaging element.
  • Still other preferred further silver halide solvents for use in connection with the present invention are thioethers as disclosed in e.g. US-P-4.960.683 and EP-A 554,585.
  • silver halide solvents are 1,2,4-triazolium-3-thiolates.
  • Combinations of different silver halide solvents can be used and it is also possible to incorporate at least one silver halide solvent into a suitable layer of the imaging element and to add at least one other silver halide solvent to the developing or activating solution. Preferably they are comprised in the alkaline processing liquid.
  • Preferred physical development nuclei for use in accordance with the present invention are sulphides of heavy metals e.g. sulphides of antimony, bismuth, cadmium, cobalt, lead, nickel, palladium, platinum, silver, and zinc.
  • sulphides of heavy metals e.g. sulphides of antimony, bismuth, cadmium, cobalt, lead, nickel, palladium, platinum, silver, and zinc.
  • Especially suitable physical development nuclei in connection with the present invention are palladium sulphide nuclei.
  • Other suitable physical development nuclei are salts such as e.g. selenides, polyselenides, polysulphides, mercaptans, and tin (II) halides.
  • Heavy metals, preferably silver, gold, platinum, palladium, and mercury can be used in colloidal form.
  • a method for obtaining an imaging element that can be used for obtaining a lithographic printing plate according to the DTR-method.
  • Said imaging element is obtained by coating on a support in the order given at least one silver halide emulsion layer in accordance with the present invention and an image receiving layer containing physical development nuclei in water permeable relationship with said silver halide emulsion layer.
  • the imaging element also comprises a base layer between the support and the silver halide emulsion layer as described above.
  • a further intermediate layer between the silver halide emulsion layer and the layer containing physical development nuclei may also be provided.
  • a matting agent is preferably included in said base layer and optionally in small amounts i.e. from 1 to 20% by weight in the silver halide emulsion layer.
  • the matting agent is included in the silver halide emulsion layer it is preferable added to the silver halide emulsion after spectral sensitization of the silver halide emulsion to avoid adsorption of the sensitizer to the matting agent.
  • Suitable matting agents for use in accordance with the present embodiment are water insoluble inorganic or organic particles having an average diameter between 1 ⁇ m and 10 ⁇ m most preferably between 4 ⁇ m and 8 ⁇ m.
  • a preferred matting agent is silica.
  • the layer containing physical development nuclei is preferably free of hydrophilic binder but may comprise small amounts up to 30% by weight of the total weight of said layer of a hydrophilic colloid e.g. polyvinyl alcohol to improve the hydrophilicity of the surface.
  • a hydrophilic colloid e.g. polyvinyl alcohol to improve the hydrophilicity of the surface.
  • Preferably used supports in connection with the present embodiment are paper supports or resin supports e.g. polyester film supports.
  • the above described DTR-imaging element is information-wise exposed using a scanning exposure and is subsequently developed with an alkaline processing liquid in the presence of developing agent(s) and silver halide solvent(s).
  • Said development step is preferably followed by a neutralization of the surface of the imaged element by guiding the element through a neutralization liquid having a pH between 4 and 7.
  • the neutralization liquid preferably contains a buffer e.g. a phosphate buffer, a citrate buffer or mixture thereof.
  • the neutralization solution can further contain bactericides, e.g. phenol, thymol or 5-bromo-5-nitro-1,3-dioxan as described in EP-150,517, wetting agents e.g.
  • the liquid can also contain substances which influence the hydrophobic / hydrophilic balance of the printing plate obtained after processing of the DTR element, e.g. silica.
  • the neutralization solution can contain wetting agents, preferably compounds containing perfluorinated alkyl groups.
  • the alkaline processing liquid and/or neutralization liquid preferably contain one or more hydrophobizing agents, e.g. those described in US-P-3,776,728, and US-P-4,563,410.
  • Preferred hydrophobizing agents are mercapto-1,3,4-thiadiazoles as described in DE-A 1,228,927 and in US-P 4,563,410, 2-mercapto-5-alkyl-oxa-3,4-diazole and long chain (at least 5 carbon atoms) alkyl substituted mercaptotetrazoles.
  • Particularly preferred compounds are 5-n-heptyl-2-mercapto-1,3,4,-oxadiazol and 3-mercapto-4-acetamido-5-n-heptyl-1,2,4-triazole.
  • an imaging element that can be used for obtaining a lithographic printing plate according to the DTR-method by coating in the order given on a hydrophilic surface of a support (i) an image receiving layer containing physical development nuclei and (ii) a photosensitive layer comprising a photosensitive silver halide emulsion in accordance with the present invention, said photosensitive layer being in water permeable relationship with said image receiving layer.
  • said imaging element may be imaged using an information-wise exposure as described above followed by a development step in the presence of development agent(s) and silver halide solvent(s) so that a silver image is formed in the physical development nuclei layer.
  • the imaging element is treated to remove the layer(s) on top of the image receiving layer, preferably by rinsing the imaging element with water, thereby exposing the imaged surface of the support by uncovering said silver image formed in said image receiving layer.
  • the hydrophobic character of the silver image is preferably improved using a finishing liquid comprising hydrophobizing agents as described above.
  • hydrophilic layers for this purpose are layers comprising a hydrophilic non-proteinic film-forming polymers e.g. polyvinyl alcohol, polymer beads e.g. poly(meth)acrylate beads or mixtures thereof.
  • a hydrophilic non-proteinic film-forming polymers e.g. polyvinyl alcohol, polymer beads e.g. poly(meth)acrylate beads or mixtures thereof.
  • Such type of layers are disclosed in EP-A-483415 and EP-A-410500.
  • a gelatin silver halide emulsion I was prepared using the double jet precipitation by slowly mixing whilst stirring 975 ml of an aqueous solution of AgNO 3 having a concentration of 2 mole/l, and 1353 ml of an aqueous solution having a concentration of 1.7 mole/l of NaCl and 0.48 mole/l of KBr. Before the precipitation 5*10 -7 mole of sodium hexachlororhodate and 1*10 -6 mole of sodium hexachloroiridate was added to the alkali halide solution.
  • the temperature during the silver halide formation was 55°C, the pH was 4.6 and the pCl 0.03.
  • the silver halide emulsion was left standing for 10 minutes more at the same temperature, pH and pCl.
  • the grain size distribution of the silver halide emulsion was measured giving the following results, clearly demonstrating that the physical ripening of the silver halide emulsion was indisputably ended at last at 5 minutes after the end of the silver halide formation : time (min) number average of grain size standard deviat. 1 0.334 ⁇ m 0.099 5 0.351 ⁇ m 0.104 9 0.348 ⁇ m 0.102
  • the obtained core-shell silver halide emulsion was cooled, flocculated and washed.
  • Gelatin was added in an amount sufficient to reach a ratio of 2/3 by weight of gelatin to silver halide, expressed as equivalent amount of silver nitrate.
  • Gelatin silver halide emulsions II and III were prepared as gelatin silver halide emulsions I wherein however no sodium hexachloroiridate was added to the alkali halide solution but 1*10 -6 mole or 4*10 -6 mole of sodium hexachloroiridate was added to the silver halide emulsion at 9 minutes after the end of the silver halide formation.
  • the silver halide emulsions I to III were red sensitised using a red sensitizing dye. Finally the silver halide emulsions I to III were stabilized by 1-phenyl-5-mercapto-tetrazole.
  • a base layer coating solution was prepared having the following composition: gelatin 5.5% carbon black 0.76% silica particles (5 ⁇ m) 1.6%
  • the silver halide emulsion coating solutions I to III were respectively coated simultaneously with the base layer coating solution by means of the cascade coating technique to a polyethylene terephthalate support provided with a pack of two backing layers such that the base layer coating was coated directly to the side of the support opposite to the side containing said backing layers.
  • the silver halide emulsion layers were coated such that the silver halide coverage expressed as AgNO 3 was 1.5g/m 2 and the gelatin content was 1.5g/m 2 .
  • the silver halide emulsion layers further contained 0.15g/m 2 of 1-phenyl-4,4'-dimethyl-3-pyrazolidone and 0.25g/m 2 of hydroquinone.
  • the base layer was coated such that the amount of gelatin in the coated layer was 3g/m 2 .
  • the layer nearest to the support of the backing layer pack contained 0.3 g/m 2 of gelatin and 0.5 g/m 2 of the antistatic agent co(tetraallyloxyethane / methacrylate / acrylic acid-K-salt) polymer.
  • the second backing layer contained 4 g/m 2 of gelatin, 0.15 g/m 2 of a matting agent consisting of transparent spherical polymeric beads of 3 micron average diameter according to EP-A-080,225, 0.05 g/m 2 of hardening agent triacrylformal and 0.021 g/m 2 of wetting agent F 15 C 7 -COONH 4 .
  • the thus obtained elements were dried and subjected to a temperature of 40 o C for 5 days and then the silver halide emulsion layers were overcoated with a layer containing PdS as physical development nuclei, hydroquinone at 0.4g/m 2 and formaldehyde at 100mg/m 2 .
  • the above described imaging elements 1 to 3 were image-wise exposed in a HeNe laser image setter and processed with the above described activator for 10 seconds at 30°C, subsequently neutralized at 25 o C with the neutralization solution described above and dried.
  • the printing plates thus prepared were mounted on the same offset printing machine HEIDELBERG GTO-46, marketed by Heidelberg, A.G., Germany, and were printed under identical conditions.
  • the above mentioned dampening solution was used at a 5 % concentration for fountain solution.
  • K+E 125 ink,marketed by Kast+Ehinger, A. G., Germany, and a compressible rubber blanket were used in each case.
  • the sensitometric properties of the developed imaging elements were characterized by the sensitivity (S), reflection density in the image areas (D max ) and non-image areas (D min ), the gradation measured by the maximum gradient of the sensitometric curve (G 1), the gradation measured in the toe of the sensitometric curve between 10 % and 25 % of the density difference (G 2),and the gradation measured in the shoulder of the sensitometric curve between 75 % and 95 % of the density difference (G 3).
  • S sensitivity
  • D max reflection density in the image areas
  • D min the gradation measured by the maximum gradient of the sensitometric curve
  • G 2 the gradation measured in the toe of the sensitometric curve between 10 % and 25 % of the density difference
  • G 3 the gradation measured in the shoulder of the sensitometric curve between 75 % and 95 % of the density difference
  • Samples 1 to 3 were used to print as described above and their lithographic properties were evaluated. All three samples could be used to print more than 10000 copies with no adverse effect on the obtained prints.

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  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Claims (10)

  1. Ein Verfahren zum Erhalt eines fotografischen Materials durch Überziehen eines Trägers mit wenigstens einer Schicht mit wenigstens einer lichtempfindlichen Silberhalogenidemulsion, deren Herstellung die folgenden Stufen umfaßt : (i) die Herstellung einer Silberhalogenidemulsion durch Fällung von Silberhalogenidkristallen in einem wäßrigen Medium, (ii) die physikalische Reifung der Silberhalogenidemulsion, (iii) die Entsalzung der Silberhalogenidemulsion und (iv) die chemische Reifung der Silberhalogenidemulsion, wobei die Silberhalogenidkristalle der lichtempfindlichen Silberhalogenidemulsion wenigstens 60 mol-% Silberchlorid, Silberbromid in einer Menge zwischen 2 mol-% und 40 mol-% und Silberiodid in einer Menge zwischen 0 mol-% und 1 mol-% enthalten, dadurch gekennzeichnet, daß der Silberhalogenidemulsion zwischen dem Ende der physikalischen Reifung und dem Ende der chemischen Reifung bei einem pH zwischen 4 und 6,5, einem pCl zwischen -0,3 und 1 und bei einem Gewichtsverhältnis von Gelatine zu als eine äquivalente Menge Silbernitrat aus gedrücktem Silberhalogenid zwischen 0,05 und 0,5 eine wasserlösliche Iridiumverbindung zugesetzt wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die wasserlösliche Iridiumverbindung zwischen dem Ende der physikalischen Reifung und der Entsalzung der Silberhalogenidemulsion zugesetzt wird.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die wasserlösliche Iridiumverbindung in einer Menge zwischen 10-7 und 10-5 Mol pro Mol AgNO3 zugesetzt wird.
  4. Verfahren nach irgendeinem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Silberhalogenidkristalle zum Kern-Hülle-Typ gehören und wesentlich die Gesamtmenge Bromid im Kern konzentriert ist.
  5. Verfahren nach irgendeinem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Silberhalogenidemulsion eine rhodiumhaltige Verbindung in einer Menge zwischen 10-8 und 10-3 Mol pro Mol AgNO3 zugesetzt wird.
  6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die rhodiumhaltige Verbindung während der Fällungsstufe der Silberhalogenidemulsion dieser Emulsion zugesetzt wird.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß die rhodiumhaltige Verbindung zwischen der Zugabe von 2 mol-% und 35 mol-% des Silbersalzes der Silberhalogenidemulsion zugesetzt wird.
  8. Verfahren nach irgendeinem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß auf den Träger ebenfalls eine physikalische Entwicklungskeime enthaltende, in wasserdurchlässiger Beziehung zur Silberhalogenid-Emulsionsschicht stehende Bildempfangsschicht vergossen ist.
  9. Ein Verfahren zum Erhalt einer Offsetdruckplatte nach dem Silbersalz-Diffusionsübertragungsverfahren, das die folgenden Stufen umfaßt :
    die informationsmäßige Abtastbelichtung eines nach dem Verfahren von Anspruch 8 erhaltenen bilderzeugenden Elements, wobei die lichtempfindliche Silberhalogenid-Emulsionsschicht unter der physikalische Entwicklungskeime enthaltenden Bildempfangsschicht aufgetragen ist,
    und die Entwicklung des bilderzeugenden Elements unter Verwendung einer alkalischen Verarbeitungsflüssigkeit in Gegenwart einer oder mehrerer Entwicklersubstanzen und eines oder mehrerer Silberhalogenid-Lösungsmittel.
  10. Ein Verfahren zum Erhalt einer Offsetdruckplatte nach dem Silbersalz-Diffusionsübertragungsverfahren, das die folgenden Stufen umfaßt :
    die informationsmäßige Abtastbelichtung eines nach dem Verfahren von Anspruch 8 erhaltenen bilderzeugenden Elements, wobei der Träger eine hydrophile Oberfläche hat und die lichtempfindliche Silberhalogenid-Emulsionsschicht auf der physikalische Entwicklungskeime enthaltenden Bildempfangsschicht aufgetragen ist,
    den Auftrag einer wäßrigen alkalischen Lösung auf das bilderzeugende Element in Gegenwart einer oder mehrerer Entwicklersubstanzen und eines oder mehrerer Silberhalogenid-Lösungsmittel, um in der Bildempfangsschicht ein Silberbild zu erzeugen,
    die Verarbeitung des bilderzeugenden Elements, um die auf der Bildempfangsschicht befindliche(n) Schicht(en) zu entfernen, wodurch die bebilderte Oberfläche des Trägers und somit das in der Bildempfangsschicht erzeugte Silberbild aufgedeckt werden.
EP19950200646 1994-04-19 1995-03-17 Verfahren zru herstellung eines photographischen Materials, das zur Verwendung in Phototypieanwendungen geeignet ist Expired - Lifetime EP0679934B1 (de)

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EP94201072 1994-04-19
EP19950200646 EP0679934B1 (de) 1994-04-19 1995-03-17 Verfahren zru herstellung eines photographischen Materials, das zur Verwendung in Phototypieanwendungen geeignet ist

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DE68922495T2 (de) * 1989-10-20 1995-11-09 Agfa Gevaert Nv Verfahren zur Herstellung einer Flachdruckplatte.
JPH06110148A (ja) * 1992-04-30 1994-04-22 Eastman Kodak Co 乳剤の相反則不軌の低減方法およびその方法により製造されたハロゲン化銀乳剤を含んでなる写真要素

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